1. Field of the Invention
The present invention pertains to photoimaging and, in particular, the use of photoresists (positive-working and/or negative-working) for imaging in the production of semiconductor devices. The present invention also pertains to novel fluorine-containing polymer compositions having high UV transparency (particularly at short wavelengths, e.g., 157 nm) which are useful as base resins in resists and potentially in many other applications.
2. Description of Related Art
Polymer products are used as components of imaging and photosensitive systems and particularly in photoimaging systems such as those described in Introduction to Microlithography, Second Edition by L. F. Thompson, C. G. Willson, and M. J. Bowden, American Chemical Society, Washington, D.C., 1994. In such systems, ultraviolet (UV) light or other electromagnetic radiation impinges on a material containing a photoactive component to induce a physical or chemical change in that material. A useful or latent image is thereby produced which can be processed into a useful image for semiconductor device fabrication.
Although the polymer product itself may be photoactive, generally a photosensitive composition contains one or more photoactive components in addition to the polymer product. Upon exposure to electromagnetic radiation (e.g., UV light), the photoactive component acts to change the rheological state, solubility, surface characteristics, refractive index, color, electromagnetic characteristics or other such physical or chemical characteristics of the photosensitive composition as described in the Thompson et al. publication supra.
For imaging very fine features at the submicron level in semiconductor devices, electromagnetic radiation in the far or extreme ultraviolet (UV) is needed. Positive working resists generally are utilized for semiconductor manufacture. Lithography in the UV at 365 nm (I-line) using novolak polymers and diazonaphthoquinones as dissolution inhibitors is a currently established chip technology having a resolution limit of about 0.35-0.30 micron. Lithography in the far UV at 248 nm using p-hydroxystyrene polymers is known and has a resolution limit of 0.35-0.18 nm. There is strong impetus for future photolithography at even shorter wavelengths, due to a decreasing lower resolution limit with decreasing wavelength (i.e., a resolution limit of 0.18-0.12 micron for 193 nm imaging and a resolution limit of about 0.07 micron for 157 nm imaging). Photolithography using 193 nm exposure wavelength (obtained from an argon fluorine (ArF) excimer laser) is a leading candidate for future microelectronics fabrication using 0.18 and 0.13 xcexcm design rules. Photolithography using 157 nm exposure wavelength (obtained from a fluorine excimer laser) is a leading candidate for future microlithography further out on the time horizon (beyond 193 nm) provided suitable materials can be found having sufficient transparency and other required properties at this very short wavelength. The opacity of traditional near UV and far UV organic photoresists at 193 nm or shorter wavelengths precludes their use in single-layer schemes at these short wavelengths.
Some resist compositions suitable for imaging at 193 nm are known. For example, photoresist compositions comprising cycloolefin-maleic anhydride alternating copolymers have been shown to be useful for imaging of semiconductors at 193 nm (see F. M. Houlihan et al, Macromolecules, 30, pages 6517-6534 (1997); T. Wallow et al., SPIE, Vol. 2724, pages 355-364; and F. M. Houlihan et al., Journal of Photopolymer Science and Technology, 10, No. 3, pages 511-520 (1997)). Several publications are focused on 193 nm resists (i.e., U. Okoroanyanwu et al, SPIE, Vol. 3049, pages 92-103; R. Allen et al., SPIE, Vol. 2724, pages 334-343; and Semiconductor International, September 1997, pages 74-80). Compositions comprising addition polymers and/or ROMP (ring-opening methathesis polymerization) of functionalized norborenes have been disclosed (e.g., PCT WO 97/33198 (Sep. 12, 1997) to B. F. Goodrich). Homopolymers and maleic anhydride copolymers of norbornadiene and their use in 193 nm lithography have been disclosed (J. Niu and J. Frechet, Angew. Chem. Int. Ed., 37, No. 5, (1998), pages 667-670). Copolymers of flourinated alcohol-substituted polycyclic etylenically unsaturated comonomer and sulfur dioxide that are suitable for 193 nm lithography have been reported (see H. Ito et al., xe2x80x9cSynthesis and Evaluation of Alicyclic Backbone Polymers for 193 nm lithographyxe2x80x9d, Chapter 16, ACS Symposium Series 706 (Micro- and Nanopatterning Polymers) pages 208-223 (1998), and H. Ito et al., Abstract in Polymeric Materials Science and Engineering Division, American Chemical Society Meeting, Volume 77, Fall Meeting, Sep. 8-11, 1997, held in Las Vegas, Nev.) Because of the presence of repeat units derived from sulfur dioxide in this alternating copolymer, it is not suitable for 157 nm lithography due to the excessively high absorption coefficient of this polymer at 157 nm.
Photoresists containing fluorinated alcohol functional groups attached to aromatic moieties have been disclosed (see K. J. Przybilla et al., xe2x80x9cHexafluoroacetone in Resist Chemistry: A Versatile New Concept for Materials for Deep UV Lithographyxe2x80x9d, SPIE Vol. 1672, (1992), pages 500-512). While suitable for 248 nm lithography, these resists, because of the aromatic functionality contained in them, are unsuitable for lithography at 193 or 157 nm (due to the excessively high absorption coefficients of the aromatic resist components at these wavelengths).
Resist compositions suitable for imaging at 157 nm are presently unknown. The main reason for this current status of 157 nm resists is that most or all known materials absorb to a significant degree at this wavelength to preclude their use as component(s) in 157 nm resists.
Copolymers of fluoroolefin monomers and cyclic unsaturated monomers are known (U.S. Pat. Nos. 5,177,166 and 5,229,473 to Daikin Industries, Ltd.). These patents do not disclose the use of these copolymers in any photosensitive compositions. Copolymers of certain fluorinated olefins with certain vinyl esters are known. For example, the copolymer of TFE with cyclohexanecarboxylate, vinyl ester is known (Japanese Patent Appl. JP 03281664 to Dainippon Ink and Chemicals). Copolymers of TFE and vinyl esters, such as vinyl acetate, and use of these copolymers in photosensitive compositions for refractive index imaging (e.g., holography) is known (U.S. Pat. No. 4,963,471 to DuPont).
Certain copolymers of fluorinated alcohol comonomers with other comonomers have been reported in U.S. Pat. No. 3,444,148 and JP 62186907 A2 patent publication. These patents are directed to membrane or other non-photosensitve films or fibers, and neither has any teaching of fluorinated alcohol comonomers use in photosensitve layers (e.g., resists).
U.S. Pat. No. 5,655,627 discloses a process for generating a negative tone resist image by coating a silicon wafer with a copolymer resist solution of pentafluoropropyl methacrylate-t-butyl methacrylate in a solvent, and then exposing at 193 nm and developing with a carbon dioxide critical fluid.
There is a critical need though for other novel resist compositions for use at 193 nm, and particularly at 157 nm, or lower that have not only high transparency at these short wavelengths but also suitable other key properties, including good plasma etch resistance and adhesive properties.
The invention in some embodiments comprises a photoresist comprising:
(a) a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; and
(b) at least one photoactive component;
wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 xcexcmxe2x88x921 at a wavelength of 157 nm.
The invention is also a process for preparing a photoresist image on a substrate comprising, in order:
(W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
(a) a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10, and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 xcexcmxe2x88x921 at a wavelength of 157 nm;
(b) at least one photoactive component; and
(c) a solvent;
(X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
(Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas; and
(Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
In another embodiment, the invention is a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10.
In another embodiment, the invention is a photoresist comprising:
(a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; and
(b) at least one photoactive component;
wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of  less than 365 nm.
In another embodiment, the invention is a process for preparing a photoresist image on a substrate comprising, in order:
(W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
(a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rf are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
(b) at least one photoactive component; and
(c) a solvent;
wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of  less than 365 nm;
(X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
(Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas; and
(Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
In another embodiment, the invention is a photoresist comprising:
(a) a fluorine-containing copolymer comprising:
(i) a repeat unit derived from at least one ethylenically unsaturated compound containing at least three fluorine atoms covalently attached to two ethylenically unsaturated carbon atoms; and
(ii) a repeat unit derived from an ethylenically unsaturated compound comprised of a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; and
(b) at least one photoactive component;
wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of  less than 365 nm.
In another embodiment, the invention is a process for preparing a photoresist image on a substrate comprising, in order:
(W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
(a) a fluorine-containing copolymer comprising:
(i) a repeat unit derived from at least one ethylenically unsaturated compound containing at least three fluorine atoms covalently attached to two ethylenically unsaturated carbon atoms that make-up a carbon-carbon double bond; and
(ii) a repeat unit derived from an ethylenically unsaturated compound comprised of a fluoroalcohol functional group having the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
(b) at least one photoactive component; and
(c) a solvent;
wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of  less than 365 nm;
(X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
(Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas; and
(Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
In yet another embodiment, the invention is a photoresist comprising:
(a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
xe2x80x94XCH2C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; and X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous, other Group Va element, and other Group VIa element; and
(b) at least one photoactive component;
wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of  less than 365 nm.
In another embodiment, the invention is a process for preparing a photoresist image on a substrate comprising, in order:
(W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
(a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
xe2x80x94XCH2C(Rf)(Rfxe2x80x2)OH
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous, other Group Va element, and other Group VIa element; and wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of  less than 365 nm;
(b) at least one photoactive component; and
(c) a solvent;
(X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
(Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas; and
(Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
In still another embodiment, the invention is a fluorine-containing polymer comprising the structure: 
wherein each of R1, R2, R3, and R4 independently is hydrogen, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic ester or a functional group containing the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)ORb
wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; Rb is hydrogen or an acid- or base-labile protecting group; p is the number of repeat units in the polymer; r is 0-4; at least one of the repeat units has a structure whereby at least one of R1, R2, R3, and R4 contains the structure C(Rf)(Rfxe2x80x2)ORb; and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 xcexcmxe2x88x921 at a wavelength of 157 nm.
In another embodiment, the invention is a photoresist comprising:
(a) a fluorine-containing polymer comprising the structure: 
xe2x80x83wherein each of R1, R2, R3, and R4 independently is hydrogen, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester or a functional group containing the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)ORb
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; Rb is hydrogen or an acid- or base-labile protecting group; p is the number of repeat units in the polymer; r is 0-4; at least one of the repeat units has a structure whereby at least one of R1, R2, R3, and R4 contains the structure C(Rf)(Rfxe2x80x2)ORb; and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 xcexcmxe2x88x921 at a wavelength of 157 nm; and
(b) at least one photoactive component.
In another embodiment, the invention is a process for preparing a photoresist image on a substrate comprising, in order:
(W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
(a) a fluorine-containing polymer comprising the structure: 
xe2x80x83wherein each of R1, R2, R3, and R4 independently is hydrogen, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester, or a functional group containing the structure:
xe2x80x94C(Rf)(Rfxe2x80x2)ORb
xe2x80x83wherein Rf and Rfxe2x80x2 are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10; Rb is hydrogen or an acid- or base-labile protecting group; p is the number of repeat units in the polymer; r is 0-4; at least one of the repeat units has a structure whereby at least one of R1, R2, R3, and R4 contains the structure C(Rf)(Rfxe2x80x2)ORb; and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 xcexcmxe2x88x921 at a wavelength of 157 nm;
(b) at least one photoactive component; and
(c) a solvent;
(X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
(Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas; and
(Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.